JP3288381B2 - Hydrocarbon ethers of sulfur-containing hydroxyl-derived aromatic hydrocarbons as synthetic lubricant base materials - Google Patents

Description

The present invention relates to sulfur-containing mono- or polyhydroxyl-derived aromatic hydrocarbon ethers, especially alkyl ethers thereof, as high performance / high temperature synthetic lubricant base stocks.

In general, current synthetic lubricants are used in the presence of antioxidants.
It has “sufficient” temperature performance with an upper limit of 0 ° C. to 260 ° C.
In the future, operating temperatures of internal combustion engines and the like will be increased to increase engine efficiency. For example, polyphenyl ethers and other hydrocarbon fluids have such higher operating temperatures, but are costly disadvantageous or have limited lubricant performance (eg, poor low temperature properties for polyphenyl ether). Clearly a new base fluid needs to be developed.

Sulfurized lubricant compositions are known in the art. U.S. Pat. No. 4,990,271 relates to sulfur-containing lubricating additives useful for providing antiwear, antioxidant, and friction reducing properties. U.S. Pat. No. 3,840,463 discloses the use of some metal dialkyldithiocarbamates or dithiophosphates in combination with metal-free additives containing sulfur and phosphorus.

The present application relates more particularly to high temperature, high performance synthetic lubricating base stocks, blended stocks, or sulfur containing mono- or sulfur-based materials having utility as additives for other base stock fluids or liquid fuels. It relates to a polyhydroxyl-derived aromatic alkyl ether.

It has been discovered that sulfur-containing hydroxyl-derived aromatic alkyl ethers have excellent catalyst-thermal / oxidative stability and lubricity. Catalysts including DSC (differential scanning calorimeter), RBOT (rotating cylinder (Bomb) oxidation test) and catalytic oxidation test
Thermal / oxidative testing provided results indicating that the fluid was superior to current commercial synthetic hydrocarbon fluids, including alkylated aromatics and polyol esters. Four-Ball Wear and EP tests show that the fluids of the invention
It has been shown to have abrasion and load characteristics along with excellent lubricating properties that are superior to many commercial synthetic hydrocarbon fluids.
All of these significant / excellent performance advantages include: 1) the inherently high catalytic-thermal / oxidative stability of the aryl groups, 2) the functionality of the sulfur involved, and 3).
It is believed that the benefits of antioxidant, cleansing, and lubricity benefits are directed.

The same applies to other dispersibility, detergency, fatigue resistance, fuel economy improvement and high temperature stability. In general, the performance benefits are fatigue resistance, antispalling, non-staining, antisquaking, improved additive solubility, improved load / support, extreme pressure, improved heat and Oxidation stability, friction reduction, abrasion resistance, corrosion resistance, improved washability,
Includes low and high temperature antioxidant, emulsifying / demulsifying, detergency and defoaming properties.

An ideal lubricant suitable for high temperature operation requires not only a high stability base material, but also an additive having appropriate thermal properties to maintain high temperature stability and function. Accordingly, the present invention provides a new class of molecularly designed, "structure-stabilized" synthetic lubricating base materials, novel R-S-Rs incorporated within the backbone of the structure. ₁
A synthetic lubricating base material having units (R and R ₁ are aryl or alkyl) is disclosed. These new synthetic lubricants are bisphenol sulfide (thiodiphenyl)
(BPS) and can be easily extended to other mono- or polyhydroxyl-derived sulfur-containing aromatics such as thiophenol. These compositions show good potential as high temperature fluids, as well as catalyst-thermal / oxidative stability (RBOT and catalytic oxidation tests) and lubricity (four-ball wear and
EP) shows additional performance characteristics such as antioxidant and abrasion resistance as shown by the test.

These compositions are used as lubricant fluids at 50-100% strength by weight, partial fluid replacement levels at 5-50% strength by weight,
And at levels of 0.01 to 10% by weight.

As noted above, these compositions can be used in fuels (hydrocarbyl or hydrocarbon, oxidized or alcohol-based, or mixtures thereof) to provide many of the beneficial properties described above. They can be used in the fuel at a concentration of 2.3 to 454 kg (5 to 1000 pounds) per 160,000 liters (1000 barrels) of fuel, more preferably 9 to 114 kg / 160,000 (20 to 250 pounds / 1000 barrels).

The compositions of the present invention are believed to be unique and novel. These compositions have not, to our knowledge, been used as base materials in aviation, automotive, marine and industrial applications, have not been reported, or have been used with hydrocarbons or oxidizing fuels.

Alkyl ethers of sulfur-containing aromatics are prepared via an interfacial method by reacting a hydroxyl-derived aromatic with an alkyl halide in the presence of a phase transfer catalyst as follows: Wherein R and R ₁ are hydrogen or a C _{1 to} C ₃₀ hydrocarbon group,
Preferably it is a C ₂ -C ₁₀ straight or branched hydrocarbon group and optionally contains sulfur, nitrogen and / or oxygen, X is Cl, Br, I, and the phase transfer catalyst is R ₂ R ₃ R ₄ R ₅
N ⁺ X ^- a _{is, R 2 R 3 R 4 R} 5 is C ₁ -C ₂₀ hydrocarbon group, X ^- is an anion). R and R ₁ may be the same or different. y
May be 1 to 3, but is preferably 1. R and R ₁ are usually aliphatic having a linear or branched structure. The combination of R and R ₁ is very important to give satisfactory viscosity properties. Other methods of making similar ethers can be used to make the compositions of the present invention and are found in the chemical literature. Para-substituted thiodiphenols are shown for illustrative purposes only.
Crosslinking can be of any degree, ortho or para or both. Some monoether may also be present and may be advantageous. Thus, other isomers such as the related sulfur-containing hydroxy-substituted aromatics can also be used. Mixtures can be used, and in some cases are preferred for more pure raw materials. The compounds of the present invention can also be prepared by direct esterification of S-containing phenols, olefins or other ether-forming species.

All suitable hydroxyl-derived sulfur-containing aromatic compounds can be used. Included in this group are compounds such as sulfurized bisphenols, thiophenols, bisphenols (eg, bisphenol A).

All suitable halogenated hydrocarbons can be used, but alkali halides are preferred. Suitable halides are 2-methylbutyl bromide, 2-ethylhexyl bromide, n-bromide
-Butyl, 2-butyl bromide, octyl bromide, decyl bromide, cyclohexyl bromide, or their corresponding chlorides, and the like.

Suitable phase transfer catalysts that promote the reaction and improve yield include benzyltriethylammonium chloride, tetrabutylammonium bromide, cyclic polyethers, poly (ethylene oxide), polyether-amines (amines are tertiary amines) Or quaternary ammonium salts such as, but not limited to, mixtures thereof. Preferred are tri- or tetra-hydrocarbon ammonium chlorides or bromides such as tricaprylyl-methylammonium chloride, tetrabutylammonium bromide.

The reaction conditions according to the present invention can vary widely depending on the particular reactants and the presence or absence of a solvent and the like. All reaction conditions known in the art can be used. Generally, stoichiometric amounts of the reactants are used. However, equimolar, less than or greater than equimolar amounts can be used. More specifically, one reactant or another reactant may be used in excess,
Less or greater molar amounts of either the phenol, amine, or carbonyl coupling agent can be used. Reaction temperatures can vary from ambient to 250 ° C., pressures can vary from ambient or less than native to 7000 kPa (1000 psig), and the molar ratio of reactants preferably varies from 5: 1 mol to 1: 5 mol.

If necessary, a suitable hydrocarbon solvent may be used. Suitable solvents include all convenient hydrocarbon solvents such as toluene and hexane.

The additives embodied herein are utilized in the lubricating oil or grease composition in an amount that imparts significant wear resistance to the oil or grease and reduces the friction of the engine running with the oil in the crankcase. A concentration of 0.001 to 10% by weight, based on the total weight of the composition, can be used. Preferably, this concentration is between 0.1 and 3% by weight when used as an additive. These compositions can also be used as lubricating fluids containing 10-99 +% by weight of reaction products. These can be used in admixture with mineral oils and / or other synthetic fluids. Additional additives can be added to obtain improved lubricating properties.

The additive may include various oily materials such as hydrocarbon lubricating media, which may include liquid oils in either mineral or synthetic oil form or in the form of greases in which these oils are used as vehicles. Has the ability to improve the properties of

Generally, mineral oils (paraffinic, naphthenic and mixtures thereof) used as lubricants or grease vehicles are available in all suitable lubricating viscosity ranges, for example, at 38 ° C (100 ° C).
5.8 mm ² / sec at ° F) (45SSU) ~1500mm ² / sec (6000S
SU), 7.4~55mm preferably at 99 ° C. (210 ° F) ² /
Can be in seconds (50-250 SSU). These oils can preferably have a viscosity index of ~ 95. The average molecular weight of these oils can range from 250 to 800. If the lubricant is used in the form of a grease, the lubricating oil generally balances the overall grease composition after considering the desired amount of thickener and other additive components contained in the grease composition. Used in a sufficient amount to take up.

A wide range of substances are used as thickening or gelling agents. These may include all conventional metal salts or soaps, which are dispersed in the lubricating vehicle in an amount of grease formation that provides the desired grease composition with the desired consistency. Other thickeners that can be used in the present grease formulations can consist of surface modified clays and non-soap thickeners such as silicas, aryl ureas, calcium complexes and similar materials. Generally, grease thickeners that do not melt or dissolve when used at the required temperatures in a particular environment can be used. However, in all other aspects, all materials commonly used to thicken or gel a hydrocarbon fluid to form a grease can be used to make a grease according to the present invention. The compositions of the present invention can be used as a vehicle for greases, alone or mixed with other grease vehicles.

If synthetic oils or synthetic oils used as grease lubricants or vehicles are desired over mineral oils or combinations thereof, various compounds of this type may be used successfully. Typical synthetic oils are polyisobutylene, polybutene, hydrogenated polydecene, polypropylene glycol, polyethylene glycol, trimethylpropane ester, neopentyl and pentaerythritol esters, di (2-ethylhexyl) sebacate, di (2-ethylhexyl) adipate, Dibutyl phthalate, fluorocarbon, silicate ester, silane, ester of phosphorus-containing acid, liquid urea, ferrocene derivative, hydrogenated synthetic oil, chain type polyphenyl, siloxane and silicone (polysiloxane), butyl-substituted bis (p-phenoxy) Phenyl) ethers, including, but not limited to, alkyl-substituted diphenyl ethers, as well as phenoxyphenyl ethers.

However, it should be understood that the composition may also include other substances. For example, corrosion inhibitors, extreme pressure agents, low temperature property modifiers and the like can be used, each of which is exemplified by non-metallic or metallic salts of metal phenates or sulfonates, polymeric succinimides, phosphorodithionates, respectively. Is done. These materials do not diminish the value of the compositions of the invention, but serve to impart their customary properties to the particular composition in which they are incorporated. These substances are engine oil,
It can be used in marine oils, aircraft lubricants, industrial gears, compressors, roads, hydraulics, and other lubricating applications and selected fuels.

The following examples are illustrative only and are not meant to be limiting.

Example 1 A mixture of 2-methylbutyl bromide (151 g) and 2-ethylhexyl bromide (193 g) was subjected to nitrogenation at 70 ° C., and bisphenol sulfide (218 g), KOH (150 g, 85%) and tetrabutyl bromide were used. To an aqueous mixture containing ammonium (10 g) and water (150 g) was added in portions with stirring. The resulting mixture was stirred and maintained at 70 ° C. for 24 hours and cooled to ambient temperature at the end of the reaction. Add almost 200g of water,
Separation gave a crude liquid product. This liquid
Wash three times with 100 mL of water, remove the light fraction at 160 ° C., 1 Torr, and then filter through alumina (neutral) to give a clear, colorless liquid (395 g) in high yield. I got it. The product was further characterized by GC, GC / MS and IR. Kv ＠ 100:
= 5.8 mm ² / s, VI = 45, pour point = -34 ° C..

Example 2 A mixture of alkyl halides [butyl bromide (137 g),
All procedures were as in Example 1 except that hexyl bromide (165 g), octyl bromide (193 g) and 2-ethylhexyl bromide (193 g) were used. The product is Kv
＠ 100: = 5.8 mm ² / sec, VI = 74 and pour point = −49 ° C.

Example 3 All procedures were as in Example 1, except that the mixture of alkyl halides was 2-ethylhexyl bromide (193 g) and decyl bromide (221 g). These products were solid state dialkylthiodiphenol ethers (by Gc).

Example 4 A mixture of alkyl halides was 2-ethylhexyl bromide (193 g), octyl bromide (68.9 g), decyl bromide (73.
6g) and dodecyl bromide (78.3g)
All procedures were similar to Example 1. The product was a solid state dialkylthiodiphenol ether (by Gc).

Evaluation of product Using the sulfurized alkyl bisphenol obtained as described above as a high-performance base material, a differential scanning calorimeter (DSC)
Table 3), the catalytic oxidation test and the rotary oxidation bomb oxidation test (Table 1), and the four-ball wear and EP test (Table 2). The thermal / oxidative stability and lubricity of these ethers were compared to commercial synthetic lubricant base stocks. The use of these ethers as a blend / additive component (1-30%) was further tested by the 4-ball abrasion test (Table 3).

In a differential scanning calorimeter test (DSC), the environment of a sample is heated or cooled at a linear rate (ie, the "scan" portion). During the scan, the uptake or release of energy by the sample was compared quantitatively (ie, calorimetrically) with the inert material (ie, differentially). Here it is used to initiate the oxidation of the test substance. For more information, see Walker et al., SAE Technical Report Series No. 801383, "Characterization of Lubricating Oils by Differential Scanning Calorimetry," pages 20-23 (October 1980), and December 7, 1970.
Journa, part of a presentation made at the ASTM D-2 Symposium in Dallas, Texas, Japan
of the Institute of Petroleum, Vol. 57, No. 558, 355
See "Characterization of Lube and Fuel Oils by DSC" (Impreial Oil Enterprises Ltd., Ontario, Canada) by F. Noel, pp. 358 (November 1971).

The catalytic oxidation test is summarized as follows: basically, the lubricant is exposed to a stream of air (5 l / h) that is bubbled through the oil formulation at 163 ° C. (325 ° F.) for 40 hours. . Present in the composition are samples of metals commonly used in engine construction, namely iron, copper, aluminum and lead. More specifically, U.S. Pat.
See 2,980.

The rotating drum oxidation test, identified as ASTM D2272, can be summarized as follows: This test method is a rapid tool for assessing the oxidation stability of (turbine) oil. The test oil, water and copper catalyst coil in the coated glass container are placed in a cylinder with a pressure gauge. The cylinder is generally filled with oxygen at 620 / cPa (9
Fill to a pressure of 0 psi) and place in a constant temperature oil bath and spin at a 30 degree angle from horizontal at 100 rpm to axial aroma. The time for the test oil to react with a fixed volume of oxygen is measured. The end of that time is indicated by a particular drop in pressure.

The four-ball abrasion test is according to ASTM D2266, see also US Pat. No. 4,761,482 for details. The K factor is determined as follows.

Wear coefficient K Unitless K is K = VH / dw (where V = wear volume, mm3 H = hardness 725 kg / mm2 for 52100 steel d = (23.3 mm / rev) (RPM × time) W = (0.408) ) (Load in kg)). The wear volume V is calculated from the wear scar diameter in mm as follows: V = [15.5D ³ −0.0103L] D × 10 ⁻³ mm ³ (where L is in kg) Mechanical load). This equation takes into account the elastic deformation of the steel ball. At a load of 60 kg, this equation is: V = [15.5D ³ -0.618] D × 10 ⁻³ mm ³ .

The four-ball EP test (ASTM D-2873) uses the load-wear coefficient (Load
The ultimate pressure characteristic of the lubricant is measured by Wear Index (LWI) and weld ponit or load. The test ball rotates under load at a tetrahedral position on top of three stationary balls submerged in lubricant. Flaw measurements on three stationary balls are used to measure LWI, and the weld is the load at which four balls weld to each other for 10 seconds. The higher the value, the better.

These results indicate that Example 2 can be used at lower concentrations in Fluid Y (10% Example 2) or Fluid X (30% Example 2), and has comparable resistance to that of the appropriate Example 2. It has been shown to provide abrasion.

As shown by these three tests, these sulfur-containing alkylaryl ethers provide significantly enhanced catalyst-thermal / oxidative stability, wear resistance and load-bearing properties, and are useful for aircraft, automotive, marine and industrial applications. There is significant value in developing high temperature / performance lubricant-based materials for applications. These good soft viscosities (Examples 1 and 2) have real advantages over polyphenyl ether. Polyphenyl ether is commercially expensive,
It is a high temperature (fluid) lubricant with poor viscosity and poor low temperature properties. The novel fluid disclosed in the present invention can also be used as a blend or as an additive component to provide the benefits of sulfur addition such as antiwear. These new compositions can be readily prepared using known phase transfer catalysis techniques commercially practiced by many chemical industries or by direct addition of olefins to form the corresponding ethers.

Although the present invention has been described in terms of preferred embodiments, it is to be understood that modifications and variations may be made by and without departing from the spirit and scope of the invention, as will be readily apparent to those skilled in the art. It is. Such variations and modifications are considered to be within the scope of the claims.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C10M 107: 02 C10M 107: 02 135: 02) 135: 02) C10N 20:02 C10N 20:02 30:04 30:04 30: 08 30:08 30:10 30:10 40:25 40:25 (72) Inventor Jen, Andrew Hazelwood Lane, Marton 08053, New Jersey, United States of America 314 (72) Inventor Kramer, Ross Allen, New Jersey, United States 08648 , Lawrenceville, Woodmont Drive 10 (72) Inventor Wei, Riwen, New Jersey, USA 08502-2600, Bell Mead, Ashwood Terrace 7 (56) References JP-A-47-7167 (JP, A) JP-A-58-174678 (JP, A) JP-A-58-201897 (JP, A) 58-199876 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C10M 105/72 C10M 135/02-135/06 C10N 40:25-40:28 CA (STN) REGISTRY (STN)

Claims (8)

(57) [Claims] 1. A lubricant composition comprising a synthetic base material and additives having improved catalyst-thermal / oxidative stability, comprising: Wherein R and R ₁ are hydrogen or a C ₁ -C ₃₀ aliphatic hydrocarbon group, X is C 1, Br, I, R and R ₁ may be the same or different, and R Or at least _one of R ₁ must be a hydrocarbon group, and y is 1-3
The reaction is carried out at a temperature of ambient to 250250 ° C. under ambient to 70007000 kPa or autogenous pressure for a period of time sufficient to obtain the desired additive reaction product, the reaction being carried out in a molar ratio of reactants. The above lubricant composition comprising a sulfur-containing hydroxyl-derived aromatic hydrocarbon ether produced by a reaction carried out in an equimolar to greater than or equal to or less than equimolar to less than equimolar range. 2. The composition of claim 1, wherein the composition further comprises an oil of lubricating viscosity selected from mineral oil, synthetic oil, or a mixture of mineral and synthetic oil. 3. A lubricant composition according to claim 2, wherein the synthetic lubricant base stock is mixed with an oil selected from alkylated aromatics, polyalphaolefins and mineral oils. 4. The method according to claim 1, wherein the additive is present in an amount of 0.001 to 10% based on the total weight of the composition.
The lubricant composition of claim 1, wherein the composition is present in a weight percent. 5. The composition according to claim 1, wherein the composition comprises as an additive a lubricant containing from 10 to 30% by weight, based on the total weight of the composition, of the hydrocarbon ether added to the oil of lubricating viscosity. object. 6. The composition according to claim 1, wherein said hydrocarbon ether is derived from a sulfur-containing phenol. 7. The composition according to claim 6, wherein said sulfur-containing phenol is a sulfurized bisphenol. 8. 10-20% by weight, based on the total weight of the composition
The composition of claim 7, further comprising other additives.